CN102101013A - Method for preparing desulfurization denitration agent, methanol and acetone by biomass pyrolysis - Google Patents
Method for preparing desulfurization denitration agent, methanol and acetone by biomass pyrolysis Download PDFInfo
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- CN102101013A CN102101013A CN201010598310XA CN201010598310A CN102101013A CN 102101013 A CN102101013 A CN 102101013A CN 201010598310X A CN201010598310X A CN 201010598310XA CN 201010598310 A CN201010598310 A CN 201010598310A CN 102101013 A CN102101013 A CN 102101013A
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Abstract
The invention belongs to the field of utilization of biomass energy, and particularly relates to a method for preparing a desulfurization denitration agent, methanol and acetone by biomass pyrolysis. The preparation method comprises the following steps of: performing quick pyrolysis on biomass at the temperature of between 300 and 800 DEG C under limited oxygen supply or anaerobic condition, then introducing the high-temperature pyrolysis gas into a reactor filled with calcium oxide, gradually cooling the pyrolysis gas to the temperature of between 70 and 120 DEG C at enough residence time, performing the reactions such as cracking, condensation polymerization and the like under the action of the calcium oxide, performing the reactions such as adsorption, neutralization and the like on the pyrolysis gas and the calcium oxide, and finally, condensing the pyrolysis gas to room temperature and collecting a liquid product. The solid desulfurization denitration agent can be obtained after the material in the calcium oxide reactor is cooled to the room temperature, and the liquid product contains two chemicals, namely the methanol and the acetone. The production of the desulfurization denitration agent, the methanol and the acetone is realized in a thermal treatment mode by using the biomass and the calcium oxide as raw materials; and the method is low in production cost, and has important significance for the utilization of the large-scale biomass energy.
Description
Technical field
The invention belongs to the field that utilizes of biomass energy, be specifically related to the method that a kind of biomass pyrolytic prepares desulfurization denitrification agent and methyl alcohol and acetone.
Background technology
All the lived organic matters that can grow are referred to as living beings, comprise plant, animal and microorganism etc.At present, can mainly lignocellulose-like biomass for the biomass resource of development and use based on various agriculture and forestry organic waste materials.Lignocellulose-like biomass is generally by cellulose, hemicellulose and three kinds of key components of lignin, and a spot of ash content and extract composition.Living beings are under limited oxygen supply or anoxia condition fast during decomposes, can form the solid three kinds of products of gas-liquid, wherein the composition of product liquid is very complicated, mainly comprises a large amount of moisture, organic acid, aldehyde, ketone, furans, phenol type substances and big molecule oligomer.This product liquid can be used as fuel and uses, but because inferior quality has limited its application.In addition, this product liquid also can be used for the various chemicals of separation and Extraction, but owing to form very complicated (have and surpass 400 kinds material), the content of most materials is all very low, makes not only technical difficulty of separation and Extraction, and does not have good economic benefits.In order to obtain some high added value product, can introduce suitable catalyst, biomass pyrolysis process or pyrolysis gas are carried out suitable catalytic treatment, to improve the productive rate and the purity thereof of target product.
Existing coal-fired power station boiler, normal cheap lime or the lime stone of adopting realized SO
2Remove, but desulfuration efficiency also is not very high, and denitration is not had effect substantially.Recent discovers, use organic calcium salt, as calcium acetate etc., can play desulfurization off sulfide effect efficiently simultaneously, this is because after the organic calcium salt decomposes, can generate the macropore calcium oxide fine grained that has than bigger serface, helps desulfurization, and form some organic matters or corresponding free radical simultaneously, can reduce and remove NO
xYet conventional organic calcium salt price is higher, as desulfurization denitrification agent use cost costliness.
Owing to contain more organic acid in the biomass pyrolytic liquid product, existing at present scholar proposes to utilize this product liquid and calcium oxide prepared in reaction desulfurization denitrification agent.Yet, owing to exist much the organic matter that can't react with calcium oxide in the biomass pyrolytic liquid, when therefore this product liquid of general using prepares desulfurization denitrification agent, it all is the ratio of control liquid and calcium oxide, make end product still be liquid, mode by atomizing sprays in the burner hearth, realizes the out of stock purpose of desulfurization.When increasing the ratio of calcium oxide, can obtain product near the solid shape, but need to remove little molecule product liquid and make some macromolecular organic polymer carbon distributions through the mode of heating or decompression distillation, thereby obtain the solid desulfurization denitrification agent, yet in the process of heating or decompression distillation, can cause the organic matter volatilization to be polluted.
Summary of the invention
The purpose of this invention is to provide a kind of new method for preparing desulfurization denitrification agent, combined production of methanol and two kinds of chemicals of acetone directly utilize biomass pyrolytic liquid product to prepare the defectives such as environmental pollution that may cause in the solid desulfurization denitrification agent process to overcome simultaneously.
The technical scheme that technical solution problem of the present invention is adopted may further comprise the steps:
(1) with living beings under the condition of limited oxygen supply or anaerobic, under 300-800 ℃, carry out fast pyrogenation reaction, reaction time 0＜t≤60 second obtain elevated temperature heat and vent one's spleen;
(2) elevated temperature heat is vented one's spleen directly feed in the reactor that calcium oxide is housed, make pyrolysis gas, the material in the calcium oxide reactor is cooled to room temperature promptly obtains the solid desulfurization denitrification agent slowly by cao layers and progressively be cooled to 70-120 ℃;
(3) pyrolysis gas is condensed to the product liquid that room temperature promptly obtains to be rich in methyl alcohol and acetone.
In the described step (1), the heating rate that biomass material is warming up to its pyrolysis reaction temperature is 10
2-10
5℃/s.
Described biological material is crushed to particle diameter before pyrolysis processing be particle below the 5mm.
Described biological material is terrestrial plant, water plant, organic garbage of city, the human and animal excreta of lignocellulose-containing, and raw material uses preceding through natural air drying.
In the described step (1), the temperature of fast pyrogenation reaction is preferably 400-700 ℃.
Described limited oxygen supply is meant the oxygen supply equivalent proportion less than 0.1 situation, and the ratio of promptly actual oxygen-supplying amount and theoretically complete combustion oxygen demand is less than 0.1; Described oxygen free condition is meant inertia anaerobic protective gas environmental condition.
In the described step (2), the reactor that calcium oxide is housed is fixed bed reactors, and the thickness of cao layers is preferably 0.1-1m.
In the described step (2), the preferable flow rate that elevated temperature heat is vented one's spleen slowly by cao layers is 0.01-0.1m/s.
Beneficial effect of the present invention is:
The present invention proposes a kind of online method for preparing desulfurization denitrification agent, after biomass material carried out fast pyrogenation, pyrolysis gas is not carried out condensation and obtain product liquid, but directly feed in the reactor that calcium oxide is housed, elevated temperature heat is vented one's spleen with after calcium oxide contacts, wherein organic acid meeting and calcium oxide generation neutralization reaction, and phenol type substances etc. also can react with calcium oxide, polycondensation reaction all can take place on the calcium oxide surface and form big molecule coke produced and cracking reaction formation permanent gases product in various in addition organic matters, flow velocity by control pyrolysis gas also progressively lowers the temperature it, thereby reaches the purpose of abundant reaction.Because reaction such as polycondensation can make organic matter solidify, thereby obtain the solid desulfurization denitrification agent, reaction such as cracking can promote the formation of methyl alcohol and these two kinds of small organic molecules of acetone in addition.At last temperature is reduced to 70-120 ℃ pyrolysis gas and be condensed to room temperature, can obtain to be rich in the product liquid of methyl alcohol and acetone.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
The invention provides the method that a kind of biomass pyrolytic prepares desulfurization denitrification agent and methyl alcohol and acetone, the invention will be further described below in conjunction with the drawings and specific embodiments.
Percentage composition among the following embodiment is weight percentage if no special instructions.Herein, min represents branch, and s represents second.
Embodiment 1
Poplar with natural air drying is a raw material, being crushed to average grain diameter is 0.5mm, material is sent in the pyrolysis reactor of a nitrogen atmosphere, at 500 ℃ of following fast pyrogenation 20s, the pyrolysis gas that is produced feeds in the fixed bed calcium oxide reactor, bed height is 0.5m, flow velocity when pyrolysis gas leaves fixed bed reactors is 0.03m/s, and temperature is 80 ℃, and Therapy lasted is carried out 30min, last this pyrolysis gas of condensation is collected product liquid to 20 ℃ of room temperatures.
Take out material and be cooled to room temperature from the calcium oxide reactor, utilize it to carry out the desulphurization denitration experiment, the result shows that desulfuration efficiency reaches 96%, and denitration efficiency reaches 58%.
The productive rate of product liquid is 8.0%, by the gas chromatographic analysis content of methyl alcohol and acetone wherein, calculates and learns that the productive rate of these two kinds of materials is respectively 2.6% and 3.3%.
Embodiment 2
Poplar with natural air drying is a raw material; being crushed to average grain diameter is 0.5mm; material is sent in the pyrolysis reactor, and at 600 ℃ of following fast pyrogenation 10s of atmosphere of inert gases (permanent gases that obtains with experiment is a protection gas), the pyrolysis gas that is produced feeds in the fixed bed calcium oxide reactor; bed height is 0.4m; flow velocity when pyrolysis gas leaves fixed bed reactors is 0.02m/s, and temperature is 70 ℃, and Therapy lasted is carried out 30min; last this pyrolysis gas of condensation is collected product liquid to 20 ℃ of room temperatures.
Take out material and be cooled to room temperature from the calcium oxide reactor, utilize it to carry out the desulphurization denitration experiment, the result shows that desulfuration efficiency reaches 97%, and denitration efficiency reaches 60%.
The productive rate of product liquid is 7.4%, by the gas chromatographic analysis content of methyl alcohol and acetone wherein, calculates and learns that the productive rate of these two kinds of materials is respectively 2.3% and 3.3%.
Embodiment 3
Pine with natural air drying is a raw material; being crushed to average grain diameter is 0.4mm; material is sent in the pyrolysis reactor, and at 400 ℃ of following fast pyrogenation 30s of atmosphere of inert gases (permanent gases that obtains with experiment is a protection gas), the pyrolysis gas that is produced feeds in the fixed bed calcium oxide reactor; bed height is 0.5m; flow velocity when pyrolysis gas leaves fixed bed reactors is 0.02m/s, and temperature is 70 ℃, and Therapy lasted is carried out 30min; last this pyrolysis gas of condensation is collected product liquid to 20 ℃ of room temperatures.
Take out material and be cooled to room temperature from the calcium oxide reactor, utilize it to carry out the desulphurization denitration experiment, the result shows that desulfuration efficiency reaches 97%, and denitration efficiency reaches 55%.
The productive rate of product liquid is 5.5%, by the gas chromatographic analysis content of methyl alcohol and acetone wherein, calculates and learns that the productive rate of these two kinds of materials is respectively 1.7% and 2.4%.
Embodiment 4
The rice husk not broken with natural air drying is raw material; material is sent in the pyrolysis reactor; at 500 ℃ of following fast pyrogenation 15s of atmosphere of inert gases (permanent gases that obtains with experiment is a protection gas); the pyrolysis gas that is produced feeds in the fixed bed calcium oxide reactor, and bed height is 0.8m, and the flow velocity when pyrolysis gas leaves fixed bed reactors is 0.03m/s; temperature is 80 ℃; Therapy lasted is carried out 50min, and last this pyrolysis gas of condensation is collected product liquid to 20 ℃ of room temperatures.
Take out material and be cooled to room temperature from the calcium oxide reactor, utilize it to carry out the desulphurization denitration experiment, the result shows that desulfuration efficiency reaches 95%, and denitration efficiency reaches 59%.
The productive rate of product liquid is 6.4%, by the gas chromatographic analysis content of methyl alcohol and acetone wherein, calculates and learns that the productive rate of these two kinds of materials is respectively 2.1% and 2.8%.
Claims (8)
1. biomass pyrolytic prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that, may further comprise the steps:
(1) with living beings under the condition of limited oxygen supply or anaerobic, under 300-800 ℃, carry out fast pyrogenation reaction, reaction time 0＜t≤60 second obtain elevated temperature heat and vent one's spleen;
(2) elevated temperature heat is vented one's spleen directly feed in the reactor that calcium oxide is housed, make pyrolysis gas, the material in the calcium oxide reactor is cooled to room temperature promptly obtains the solid desulfurization denitrification agent slowly by cao layers and progressively be cooled to 70-120 ℃;
(3) pyrolysis gas is condensed to the product liquid that room temperature promptly obtains to be rich in methyl alcohol and acetone.
2. biomass pyrolytic according to claim 1 prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that, in the described step (1), the heating rate that biomass material is warming up to its pyrolysis reaction temperature is 10
2-10
5℃/s.
3. biomass pyrolytic according to claim 1 prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that, described biological material is crushed to particle diameter before pyrolysis processing be particle below the 5mm.
4. biomass pyrolytic according to claim 1 prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that, described biological material is terrestrial plant, water plant, organic garbage of city, the human and animal excreta of lignocellulose-containing, and raw material uses preceding through natural air drying.
5. biomass pyrolytic according to claim 1 prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that: in the described step (1), the temperature of fast pyrogenation reaction is preferably 400-700 ℃.
6. biomass pyrolytic according to claim 1 prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that, described limited oxygen supply is meant the oxygen supply equivalent proportion less than 0.1 situation, and the ratio of promptly actual oxygen-supplying amount and theoretically complete combustion oxygen demand is less than 0.1; Described oxygen free condition is meant inertia anaerobic protective gas environmental condition.
7. biomass pyrolytic according to claim 1 prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that, in the described step (2), the reactor that calcium oxide is housed is fixed bed reactors, and the thickness of cao layers is preferably 0.1-1m.
8. biomass pyrolytic according to claim 1 prepares the method for desulfurization denitrification agent and methyl alcohol and acetone, it is characterized in that, in the described step (2), the preferable flow rate that elevated temperature heat is vented one's spleen slowly by cao layers is 0.01-0.1m/s.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941428A (en) * | 2014-03-25 | 2015-09-30 | 华北电力大学 | Novel limestone-gypsum wet flue gas desulfurization additive |
| CN107243244A (en) * | 2017-06-16 | 2017-10-13 | 中国石油大学(华东) | Carbide slag and biological pyrolysis oil prepare biological desulphurization denitrfying agent and its application method |
| CN111514726A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration agent for dry-process cement kiln, use method of denitration agent and denitration system |
| CN111514738A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration water agent for dry-process cement kiln, use method of composite biomass denitration water agent and denitration system |
| CN111514739A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration powder for dry-process cement kiln, use method of composite biomass denitration powder and denitration system |
| CN111790266A (en) * | 2020-07-27 | 2020-10-20 | 山东大学 | System and method for simultaneously removing carbon dioxide and nitrogen oxide |
| CN111849526A (en) * | 2020-07-22 | 2020-10-30 | 中国电力工程顾问集团西北电力设计院有限公司 | Method for co-producing coke and phenol by pyrolyzing biomass |
| CN112169576A (en) * | 2020-10-12 | 2021-01-05 | 山东奥淼科技发展有限公司 | Ammonia-free organic dry powder denitration agent and preparation method thereof |
| CN112742205A (en) * | 2019-10-31 | 2021-05-04 | 广东万引科技发展有限公司 | Novel biomass denitration agent for dry-process cement kiln, use method of novel biomass denitration agent and denitration system |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941428A (en) * | 2014-03-25 | 2015-09-30 | 华北电力大学 | Novel limestone-gypsum wet flue gas desulfurization additive |
| CN104941428B (en) * | 2014-03-25 | 2017-08-08 | 华北电力大学 | A kind of novel lime stone gypsum wet flue gas desulfurizing additive |
| CN107243244A (en) * | 2017-06-16 | 2017-10-13 | 中国石油大学(华东) | Carbide slag and biological pyrolysis oil prepare biological desulphurization denitrfying agent and its application method |
| CN111514726A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration agent for dry-process cement kiln, use method of denitration agent and denitration system |
| CN111514738A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration water agent for dry-process cement kiln, use method of composite biomass denitration water agent and denitration system |
| CN111514739A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration powder for dry-process cement kiln, use method of composite biomass denitration powder and denitration system |
| CN111514726B (en) * | 2019-02-02 | 2024-01-26 | 广东万引科技发展有限公司 | Novel composite biomass denitration agent for dry-method cement kiln, application method of novel composite biomass denitration agent and denitration system |
| CN112742205A (en) * | 2019-10-31 | 2021-05-04 | 广东万引科技发展有限公司 | Novel biomass denitration agent for dry-process cement kiln, use method of novel biomass denitration agent and denitration system |
| CN112742205B (en) * | 2019-10-31 | 2024-01-23 | 广东万引科技发展有限公司 | Novel biomass denitration agent for dry-method cement kiln, application method of novel biomass denitration agent and denitration system |
| CN111849526A (en) * | 2020-07-22 | 2020-10-30 | 中国电力工程顾问集团西北电力设计院有限公司 | Method for co-producing coke and phenol by pyrolyzing biomass |
| CN111790266A (en) * | 2020-07-27 | 2020-10-20 | 山东大学 | System and method for simultaneously removing carbon dioxide and nitrogen oxide |
| CN112169576A (en) * | 2020-10-12 | 2021-01-05 | 山东奥淼科技发展有限公司 | Ammonia-free organic dry powder denitration agent and preparation method thereof |
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